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As compared with widely used polyolefin materials, aliphatic polyesters have been primarily used in electronics, packaging, and biomedicine owing to its unique biocompatibility and degradability. At present, ring-opening polymerization (ROP) of lactone is the main method to synthesize polyesters. Two types of catalysts, including metal-based catalysts and organocatalysts, were most researched today. However, metal-based catalysts lead to polymer materials with metal residues, which limits its properties and applications. As a result, organocatalysts have received great attention. In this review, the progress of organocatalytic ring-opening polymerization in the past decades was systematically summarized. The potential challenges and development directions in this field are also discussed.